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Multiphoton ionization photoelectron spectroscopy of acetaldehyde via the A~ 1

Summary: Multiphoton ionization photoelectron spectroscopy of acetaldehyde
via the A~ 1
A , B~ , C~ , and D~ states
Ho-Tae Kim and Scott L. Andersona)
Department of Chemistry, University of Utah, 315 S. 1400 E., Room 2020, Salt Lake City, Utah 84112-0850
Received 6 October 2000; accepted 20 November 2000
REMPI spectra are reported for the acetaldehyde A~ 1
A , B~, C~ , and D~ states. Photoelectron
spectroscopy is used to probe the nature of the intermediate states, measure the cation vibrational
frequencies, and to identify useful routes for preparing state-selected ions. Ab initio calculations of
neutral and cation vibrational frequencies are also reported. The B~ state is found to be a
well-behaved Rydberg state, but with some distortion relative to the cation geometry along the 10
and 15 coordinates. There are B~ state REMPI transitions that produce well state-selected cations,
with vibrational energies of up to 0.4 eV, and several new cation frequencies are observed. The
A~ 1
A state gives structured, if somewhat broadened, REMPI transitions, but ionizes to produce a
broad population of vibrationally hot ions. Only the origin band of the C~ state is observed in
REMPI, despite high intensity for this state in absorption. A few D~ state transitions are sharp, and
ionize to produce cold cations, as expected for a good Rydberg state. Most D~ state levels are
strongly mixed and broadened, however, and ionize to hot cations. Inconsistencies in the literature


Source: Anderson, Scott L. - Department of Chemistry, University of Utah


Collections: Energy Storage, Conversion and Utilization; Materials Science; Chemistry